Relationship between measures of fitness and time scale in evolution

The notion of fitness is central in evolutionary biology. We use a simple spatially extended predator-prey or host-pathogen model to show a generic case where the average number of offspring of an individual as a measure of fitness fails to characterize the evolutionary dynamics. Mutants with high initial reproduction ratios have lineages that eventually go extinct due to local overexploitation. We propose general quantitative measures of fitness that reflect the importance of time scale in evolutionary processes.     

Stereostructure of a novel cytotoxic 18-membered macrolactone antibiotic FD-891

The absolute stereochemistry of FD-891, a novel cytotoxic 18-membered macrolactone antibiotic, was determined by a synthetic approach as well as X-ray diffraction of degradative derivatives. The absolute configuration of FD-891 turned out to be as shown above. The stable conformer of FD-891 was also discussed with respect to biological activity by comparison with the structurally related concanamycin A on the bases of molecular mechanics calculations. [structure: see text]     

A Two-Step Synthesis Of (±)-Blastmycinolactol Using Acylurea

A convenient synthesis of natural (±)-blastmycino-lactol from the aldol addition reaction of n-pentanoylurea and (±)-2-benzyloxypropionaldehyde is described.     

Gas analyzer for continuous monitoring of trace level methanethiol by microchannel collection and fluorescence detection

The highly odorous compound methanethiol, CH₃SH, is commonly produced in biodegradation of biomass and industrial processes, and is classed as 2000 times more odorous than NH₃. However, there is no simple analytical method for detecting low parts-per-billion in volume ratio (ppbv) levels of CH₃SH. In this study, a micro gas analysis system (μGAS) was developed for continuous or near real time measurement of CH₃SH at ppbv levels. In addition to a commercial fluorescence detector, a miniature high sensitivity fluorescence detector was developed using a novel micro-photomultiplier tube device. CH₃SH was collected by absorption into an alkaline solution in a honeycomb-patterned microchannel scrubber and then mixed with the fluorescent reagent, 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (DBD-F). Gaseous CH₃SH was measured without serious interference from other sulfur compounds or amines. The limits of detection were 0.2 ppbv with the commercial detector and 0.3 ppbv with the miniature detector. CH₃SH produced from a pulping process was monitored with the μGAS system and the data agreed well with those obtained by collection with a silica gel tube followed by thermal desorption–gas chromatography–mass spectrometry. The portable system with the miniature fluorescence detector was used to monitor CH₃SH levels in near-real time in a stockyard and it was shown that the major odor component, CH₃SH, presented and its concentration varied dynamically with time.     

Sulfonyl-bridged oligo(benzoic acid)s: synthesis, X-ray structures, and properties as metal extractants

Sulfonyl-bridged oligo(benzoic acid)s 7 _n (n = 2–4) are prepared from the corresponding triflate esters (8 _n ) of sulfur-bridged oligophenols by palladium-catalyzed methoxycarbonylation of the triflate moieties, followed by hydrolysis of the resulting methyl esters, and subsequent oxidation of the sulfur bridges. X-ray analysis reveals that dimer 7 ₂ forms supramolecular zig-zag chains through intermolecular hydrogen bonds between the carboxy groups. As for the crystal of trimer 7 ₃ , two molecules are associated through two couples of intermolecular hydrogen bonds between terminal and central carboxy groups to form a cyclic dimer, which connects with two adjacent dimers with the remaining carboxy groups to construct an infinite columnar structure. Tetramer 7 ₄ adopts a monomolecular cyclic structure through intramolecular hydrogen bonds between the terminal carboxy groups, and a molecule connects with each of two adjacent molecules through two couples of intermolecular hydrogen bonds between inner carboxy and sulfonyl groups. Solvent extraction experiments reveal that the oligo(benzoic acid)s exhibit high extractability toward lanthanoid ions (Ln³⁺); the performance follows the order 7 ₄  ≈ 7 ₃  > 7 ₂ . Moderate extraction selectivity is observed for the extraction of Pr³⁺, Gd³⁺, and Yb³⁺ with 7 ₂ . X-ray crystallographic analysis of cluster [Tb₄L₄(H₂O)₆](Et₃NH)₄, which was prepared from 7 ₄ (H₄L) and Tb(NO₃)₃·6H₂O in the presence of Et₃N, reveals that no sulfonyl oxygens coordinate to the metal centers. This indicates that the high extractability of 7 ₄ originates from the electron-withdrawing nature of the sulfonyl function, which increases the acidity of two adjacent carboxy groups.     

Reductive Ring‐Opening Reaction of 2,3‐Epoxy‐1,4‐butanediones with SbCl3‐Bu4NI in the Presence of Na2S2O3·5H2O

1,4‐Disubstituted 2,3‐epoxy‐1,4‐butanediones were converted to 1,4‐disubstituted 2‐hydroxy‐1,4‐butanediones with SbCl₃‐Bu₄NI in the presence of Na₂S₂O₃ · 5H₂O. The ring opening of terminal epoxides can also be accomplished to afford the corresponding haloalcohol with SbCl₃ and tetrabutylammonium halides, Bu₄NX (X=Cl, Br, I) under the same reaction conditions.     

Electrostatic Interactions That Determine the Rate of Pseudorotation Processes in Oxyphosphorane Intermediates: Implications with Respect to the Roles of Metal Ions in the Enzymatic Cleavage of RNA

The enzymatic cleavage of RNA takes place via a cyclic pentacoordinate oxyphosphorane intermediate/transition state. We carried out ab initio investigations on the neutral cyclic oxyphosphorane, which exists as a stable intermediate. As a consequence of the conformational preferences of the pentacoordinate trigonal bipyramidal intermediates, the rotation of the P-OH bonds is strongly coupled with the reaction coordinate for the pseudorotation process. In addition, the neutral PF(4)OH species has a higher barrier to pseudorotation than the corresponding anionic species PF(4)O(-). These findings are related to the positive charge of the hydrogen atoms on the equatorial oxygens in the trigonal bipyramidal structures: the hydrogen atoms preferably adopt eclipsed positions relative to the axial ligands. Fixing the cationic species in these regions causes an increase in the barrier heights for pseudorotation processes and, thus, prevents isomerization by pseudorotation. Consequently, metal coordination in the double-metal ion mechanism for enzymatic cleavage of RNA should serve to exclusively stabilize the trigonal bipyramidal intermediate/transition state for the in-line attack and departure process.     

Development of new photocatalytic water splitting into H2 and O2 using two different semiconductor photocatalysts and a shuttle redox mediator IO3-/I-

A new type of photocatalytic reaction that splits water into H2 and O2 was designed using a two-step photoexcitation system composed of an iodate/iodide (IO3-/I-) shuttle redox mediator and two different photocatalysts, one for H2 evolution and the other for O2 evolution. Photocatalytic oxidation of water to O2 and reduction of IO3- to I- selectively proceeded with good efficiencies over TiO2-rutile and Pt-WO3 photocatalysts under UV and visible light irradiations, respectively. The O2 evolution selectively proceeded even in the presence of a considerable amount of I- in the solutions, although the oxidation of water is thermodynamically less favorable than oxidation of I-. Both the adsorption property of IO3- anions and the oxidation property of the photocatalysts are doubtless responsible for the selective oxidation of water. On the other hand, photocatalytic reduction of water to H2 and oxidation of I- to IO3- proceeded over Pt-TiO2-anatase and Pt-SrTiO3:Cr/Ta (codoped with Cr and Ta) photocatalysts under UV and visible light, respectively. The combination of two different photocatalysts results in a stoichiometric evolution of H2 and O2 via the redox cycle of IO3- and I-. The photocatalytic water splitting under visible light irradiation (lambda > 420 nm) was demonstrated by using the Pt-SrTiO3:Cr/Ta, Pt-WO3, and IO3-/I- shuttle redox mediator.     

Immunological properties of type IV collagen from mouse kidney

Some immunological properties of mouse kidney type IV collagen (MKIVC) were investigated. In enzyme-linked immunosorbent assay (ELISA), rabbit anti-MKIVC antiserum reacted strongly with MKIVC but not at all with type I collagen or laminin of mouse origin. Thus, the purified MKIVC preparation was not contaminated with detectable amounts of other constituents of the extracellular matrix and the basement membrane including interstitial collagens, as suggested previously (T. Oikawa et al., Chem. Pharm. Bull., 34, 789 (1986)). In ELISA inhibition assay, human kidney type IV collagen (HKIVC) only partially inhibited the binding of MKIVC to anti-MKIVC antiserum. Similarly, HKIVC showed a far weaker binding capacity to the antiserum compared to MKIVC in ELISA direct binding assay. After the anti-MKIVC antiserum was absorbed with acetone powder of human kidney, the resulting antiserum still possessed a considerable binding activity to MKIVC but did not react with HKIVC. In accord with these findings, anti-MKIVC antiserum immunostained both mouse and human renal basement membranes, while it stained the former but not the latter after being absorbed with human kidney. Taken together, these results suggest that MKIVC possesses at least two antigenic determinants; one but not the other cross-reacts with human kidney basement membrane collagen.     

Two‐Dimensional Perovskite Oxynitride K2LaTa2O6N with an H+/K+ Exchangeability in Aqueous Solution Forming a Stable Photocatalyst for Visible‐Light H2 Evolution

Undoped layered oxynitrides have not been considered as promising H₂‐evolution photocatalysts because of the low chemical stability of oxynitrides in aqueous solution. Here, we demonstrate the synthesis of a new layered perovskite oxynitride, K₂LaTa₂O₆N, as an exceptional example of a water‐tolerant photocatalyst for H₂ evolution under visible light. The material underwent in‐situ H⁺/K⁺ exchange in aqueous solution while keeping its visible‐light‐absorption capability. Protonated K₂LaTa₂O₆N, modified with an Ir cocatalyst, exhibited excellent catalytic activity toward H₂ evolution in the presence of I^? as an electron donor and under visible light; the activity was six times higher than Pt/ZrO₂/TaON, one of the best‐performing oxynitride photocatalysts for H₂ evolution. Overall water splitting was also achieved using the Ir‐loaded, protonated K₂LaTa₂O₆N in combination with Cs‐modified Pt/WO₃ as an O₂ evolution photocatalyst in the presence of an I₃^?/I^? shuttle redox couple.